Still on my quest for nitrate removal, I (again) found this item for sale on E-Bay.
The N-Forcer on E-Bay
But, after a search on it, I came across the following site that shows the individuals from the company who make the N-Forcer responding back and forth with another individual who has "questions" regarding the capability of the N-Forcer.
Just thought I'd share. Any comments?
On March 22nd, 1999, I got the following unsolicited email regarding my technology review of the N-Forcer:
Ellen Lubin wrote:
> Hello Greg,
>
> I take issue with the "snake oil" comment. I'm going to be at Virginia
> Poly Tech on March 28-31 talking at a conference on Fundamentals,
> Modeling, and Applications of Nitrification and Dentrification in
> Wastewater Treatment why don't you stop by and learn about our
> technology before bad mouthing it. Stop by our Industrial site
> www.upscalewater.com and take a look at the mechanism that drives our
> technology. Our technology is denitrifying drinking water in Montana,
> wastewater treatment in Miami and we are being named Best Available
> Technology for Nitrate Removal by the EPA. Eventually every drop of
> water you drink, flush down your toilet and every drop of water used in
> manufacturing will be denitrified by our N-Forcer technology. You show
> your ignorance by talking before you know what you're talking about.
>
> If after reading about our technology you have any further questions I
> would be glad to educate you on denitrification.
>
> HAVE AN INFORMATIVE DAY!
>
> Ellen Lubin, VP Sales/Mkt
This is the reply I sent in March 24th. I have yet to get a response to this.
Ms. Lubin,
Based on the information you provided, and what was available on your
website, I am again reviewing your N-Forcer technology. I have several
questions regarding the information you provided that I hope you can clear
up for me.
I have looked through the EPA website in order to find documentation
regarding an endorsement of the N-Forcer technology by the EPA and was
unable to find it. A test protocol, dated May 11th, 1998 has been adopted
entitled "Protocol for Equipment Verification Testing for Physical Removal
of Nitrate", which contained test plans for reverse osmosis, ion exchange
and biological process, but no mention was made of electrochemistry. To
date, no information appears to be published endorsing any available
nitrate removal technology as far as I was able to determine, although it
is quite possible this has in fact been done and the information has not
yet been published on the web. I would imagine that your company has
issued a press release that would give me the information I need to track
down the verification.
I would be interested in finding out what municipality in Montana is
currently using N-Forcer technology, so I could contact them and hear their
results. Although they would be operating under very different conditions
than fishkeepers, their results would probably be helpful. I'm still
tracking down what's going on with the Miami/Dade County and hope to get
some information from them soon.
I worked through the chemistry to identify the effects of N-Forcer
technology on the pH of the water column. Using the formula provided in
the electrochemistry section of your web page, it appears that in reducing
a 5 ppm concentration of nitrate, it would produce a molar OH-
concentration of .0004838, and this would shift the pH of the water from
7.0 to 10.68. I am in the process of getting verification for these
calculations, but if you have a resource there that can confirm or debunk
these calculations your input would be helpful.
I looked at the program for the conference at Virginia Tech, and didn't see
you on the speaker's list. What's your talk about?
Greg Letiecq
Sometimes, silence can speak volumes...
After posting in rec.aquaria.tech for assistance in confirming these calculations and getting input on the feasability of this process, Mark Lubin decided to weigh in with this post on March 29th:
To all N-FORCER owners, but especially to the overly critical and the
critically ignorant…I guess that means you Greg Letiecq -
There's been a lot of banter in this forum recently about the chemistry and
technology behind the product you all know as the N-FORCER. There have been
comments about the technology and a large dose of opinionating about the moral
turpitude of this company's marketing staff and its advertising efforts.
As has been pointed out, the net reaction for nitrate reduction at the cathode
is:
2NO3¯ + 6H2O + 10e¯ --> N2 + 12OH¯
The analysis offered then proceeded to determine that the effect of this
system could only be to raise the pH to 10.99. This would be true only if
the system were sealed, contained no air above or dissolved in the water, and
contained only deionized water.
Further, and more importantly, the reaction above upon which Mr. Letiecq
builds his case as to the N-FORCER's devastating effects refers only to the
nitrate reduction reaction at the cathode. Nowhere in our literature,
advertisements, or on our web pages do we claim this is the only reaction
taking place. It should be apparent to anyone with even a modest knowledge
of chemistry that this is preposterous and would lead to both mass and
electron imbalance almost instantly.
When I and my marketing staff decided what was to go out, we saw no reason to
include a complete tutorial on all aspects of aquatic chemistry or
electrochemistry. Therefore, I will comment at this time on some other
aspects of the system's operation and address why the increase in pH
described simply does not occur.
* As I noted, the 10.99 pH value is only valid in a sealed, degassed, RO or DI
water system.
* The carbonate - carbon dioxide equilibrium system is one of the main
controllers of pH according to the following reaction, found in any beginning
aquatic chemistry book:
H2O + CO2 <--> H2CO3 <--> H+ + HCO3¯ pH varies from 6.0 to 8.4
* Production of ammonia by aerobic bacteria is an acidifying oxidation. The
hydrogen ions produced are on a 1:1 basis mole for mole with nitrite as
follows:
2NH3 + 3O2 --> 2NO2¯ + 2H2O + 2H+
* The ammonia consumes oxygen as above and the nitrite ion (NO2¯ ) so
produced is oxidized to nitrate ion (NO3¯ ) also by basically using up oxygen
as follows:
2NO2¯ + O2 --> 2NO3¯
* The oxygen used in both of these reactions is oxygen dissolved in the
water, not in the gaseous form. Aside from equilibrium with atmosphere,
there are two possible anodic reactions which occur in an N-FORCER at the
anode electrode (that's the one not taken into account during the so called
scientific analysis of our system):
2H2O --> O2 + 4H+ + 4e¯
4OH¯ --> 2H2O + O2 + 4e¯
* The proprietary mixed metal oxide coating on the anode electrode
participates in maintaining electrical neutrality and also generates some H+
ions to offset the OH¯ production as follows:
M2Ox + H2O <--> M2Ox +/- n +/-ne¯ +/-nH+
What this reaction shows is that as the potential of the system is changed the
character of the anode switches back and forth among the various oxides,
hydrides, and hydroxides which the coating can form.
* Since none of the conversions described above occur all at once the possible
effects on pH are avoided because the system has more than adequate time to
equilibrate by the various buffering mechanisms.
It appears to me that Mr. Letiecq has been trying to build himself a
reputation as an "expert" in the electronic media at UpSCALE's expense by
virtue of this type of analysis and product review, yet he admittedly does
not and has not owned one of our products at any time. I resent being called
a "snake oil merchant" by someone who tries to cover his rather thin
knowledge of chemistry by making a lot of ill-informed noise and who
proclaims as "impossible" what he doesn't have the capacity to understand.
In today's edition of Mr. Letiecq's newsletter he has, to his credit, finally
picked up a chemistry book. However, he is still missing the point…not all
moles of these substances are created, used, or need to be buffered at one
time.
Perhaps THE major fault in his reasoning and arguments is that simply because
he cannot find literature references to our process it must not exist. The
processes he says he did find occur in acidic water and I'm willing to bet
what he found were entries in the table of "electrochemical half-cell
potentials" from the Handbook of Chemistry & Physics or some other
compendium. The UPSCALE process is not in the literature because WE invented
it WE have not published it, so its not generally available for other people
to employ.
Mr. Letiecq's expert friends may be very knowledgeable in their respective
fields, but they are not the inventors of this technology and are not
equipped to comment on whether or not it is possible to consummate these
reactions. They are however, far more qualified than Mr. Letiecq will ever
be.
The famous British scientist, Lord Kelvin, once said:
"Condemnation without investigation is the height of ignorance"
Since Mr. Letiecq has based his "scientific" analysis on drawing conclusions
from advertising rather than science, I submit he should pay close attention
to this quote. He seems to be suffering from a large dose of the "N.I.H"
syndrome…"Not Invented Here".
Mark Lubin, President/CEO
Of course, this post warranted a response, which I posted on March 30th:
upscale@my-dejanews.com wrote:
> To all N-FORCER owners, but especially to the overly critical and the
> critically ignorant…I guess that means you Greg Letiecq -
Overly critical and critically ignorant. Well, I'll accept that. In my
experience, being critical of marketing claims until the technology is proven
is a wise course of action. As far as my ignorance, I am doing my best at
resolving that with the help of the members of this group, the library, and
friends of mine that have a far more thorough technical background. I
repeatedly ask for help in understanding this process, but unfortunately your
VP of marketing has failed to respond to my requests. My ignorance is as much
a product of the nonresponsiveless of your company as anything else.
At least now, however, we have an open discussion on the topic where we would
hope the truth can be found. I can hope for no better outcome, and if the
technology is sound and proven, I would darn well like to know it as we all
have nitrate management issues and are always looking for solutions. I honor
the truth.
We do apparently agree that the N-Forcer process does create a number of OH-
ions that would shift the pH of pure water. Whether the carbonate buffering
system present in most freshwater compensates for this shift is somewhat
irrelevant in that this only delays the shift in pH as the process continues.
At some point, the carbonate concentration will reach a point where the pH
will shift significantly upwards. With the great deal of OH- produced, this
point can be reached rather rapidly, depending on the buffering capacity that
exists. For someone like myself, who has relatively soft water in my
aquarium, I would fear this to happen sooner rather than later.
Likewise of limited relevance is the question of how we got the initial
concentration of nitrate, and what effect that process had. The nitrate
concentrations that I experience can in no way compansate for the shift the
N-Forcer process apparently performs, as the dissociation constant of a
nitrates is extrememely low compared to the near unity dissociation constant
of hydroxide, and for every mole of nitrate six moles of hydroxide is
apparently produced. So not only is nitrate a much weaker acid than
hydroxide is a base, but there is far more hydroxide produced than nitrate
removed.
I can't see any reason to believe that the introduction of 6 moles of OH- for
every mole of nitrate removed can NOT have an effect on water chemistry. I
have modeled the effect on a admittedly simplified system, but if it will
assuage the feelings of upscale technologies I can model a more complex system
to demonstrate essentially the same thing.
I do appreciate the information on the reactions at the anode, and will take a
look at them shortly to see what effect they have. When I have some
information on that, I will do my best to describe any mitigating effects.
Admittedly, we do not have access to anything describing the process that
actually occurs. It is not described in patent application #5614078. It is
not described in any available textbook, and I cannot find a single
scientific paper that describes it. It is science, that for the scientific
community does not exist as it has not been published, reviewed by peers, or
vetted in any way. With the protection available through patent law, it
would seem to be no threat to make known exactly how this miracle of
electrochemistry is supposed to occur, yet for some reason it remains a dark
mystery.
So I have to figure out what's going on based on what Upscale Technology
chooses to provide. I've done that. Now I am apparently ignorant for not
understanding something that is considered by Upscale Technology to be a
secret. Well, educate me, correct my calculations, give me the proper
formulas.
I suppose that in the end it is more a question of whether it works rather
than how it works, but to spend $300-$450 to purchase it in order to test it
is pretty much out of the question. Since there is nothing in the way of
test data available, the only option I have is to try to understand the
process that supposedly takes place and calculate the results as best I can.
Sure I'll make mistakes, and I welcome corrections.
Greg
http://www.geocities.com/ResearchTriangle/.../2024/fish.html
And after researching the assertions of Mr. Lubin, my conclusions were posted on March 31st:
As time permits, I'm trying to make some sense out of Mark Lubin's description
of the effects that occur at the anode of the N-Forcer unit, and about what's
going on with the metal-oxide surfaces of the anode and cathode. Again, I'm
looking for some help around this.
It would seem to make sense that impacts at the anode can and would offset
the effects we've identified at the cathode. If we add OH- ions at one, and
remove them at the other, it's possible that we end up with a neutral or at
least less drastic effect. At least it would appear that the determination
of the cathode effects is essentially accurate, as Mark seems to be in
agreement with those calculations.
At the anode, Mark points out two "possible" reactions. The first appears to
be simply water electrolysis, 2H20 -> O2 + 4H+ + 4 e-. There are several
issues that are problematic here.
The first problem is that this reaction is entirely contradictory to the
process described in the patent application for the technology (PN
5,614,078). In that document, Mark describes the negative impacts of other
implementations of electrolytic processes, at one point saying "since most
noble metals are excellent catalysts for the hydrogen ion reduction reaction,
the hydrogen evolution reaction will proceed at a reaction rate many times
larger than the nitrate reduction rate, causing the pH of the sea water to
increase beyond acceptable limits for marine life survival." Essentially,
that unless the process is modified in some way, large amounts of water will
be electrolized, causing a massive pH shift. Later on in the document, when
describing the process, Mark says "In addition, carbon fibers demonstrate
poor electro-catalytic behavior for hydrogen, oxygen and chlorine reactions.
The low potential required for nitrate reduction with carbon fibers also
helps to prevent any hydrogen, oxygen, and chlorine reactions."
So in the patent application, it would seem that Mark denies any appreciable
activity on electolyzing water, but in his statements to us here, he
would appear to claim it is an important balancing process to the demonstrated
reactions occuring at the cathode. Unless I have misunderstood, this is a
complete contradiction.
The other process he claims is "possible" 4OH- -> 2H2O + O2 + 4e-. While
this correctly balances for mass and charge, it seems somewhat unusual to me
that hydroxide ions would act this way. With all of the other substances in
the water available for reaction, that hydroxide ions would "implode" like
this to generate free electrons would appear to violate the laws of
thermodynamics for conservation of energy. I have not calculated it yet, but
the Gibbs free energy of the left hand side is probably far lower than the
Gibbs free energy on the right hand side since there are free electrons
there. Since reactions tend to move from higher to lower energies, this
seems backwards, and there is no indication that the anode can provide that
energy. The patent documents talk about low current densities as an
important feature of the process, so that would seem to make this abundance
of energy unavailable. I need additional input on this part especially, and
would welcome any help any of you out there can provide.
It would have been better if Mark had told us what actually is happening,
instead of what is possibly happening. It's takes a lot of effort to vet
these different possibilities, and even if one reaction is demonstrated to be
impossible, it's an easy thing to dismiss the results as we haven't actually
determined anything about what the system in actuality does.
The last piece of technical information was this:
"The proprietary mixed metal oxide coating on the anode electrode
participates in maintaining electrical neutrality and also generates some H+
ions to offset the OH¯ production as follows:
M2Ox + H2O <--> M2Ox +/- n +/-ne¯ +/-nH+
What this reaction shows is that as the potential of the system is changed the
character of the anode switches back and forth among the various oxides,
hydrides, and hydroxides which the coating can form."
I would assume that in this equation, "M" represents the proprietary metal
used in the metal oxide. What the "n" represents is a mystery, but hopefully
it's not too difficult to solve. Since we're talking about a generic
equation here, in english it would seem to read as 'Metal oxide and water
yield metal oxide and some stuff, some stuff with electrons, and some stuff
with protons' (H+ is a fancy way of saying proton).
In any reaction, there has to be conservation of mass and charge, so we can
subtract parts out and still have a valid equality, although that no longer
represents the process. If we subtract M2Ox from both sides, we get the
following equality:
H2O = +/- n +/-ne¯ +/-nH+
The "stuff" in water is pretty well documented. H2O can dissociate into H+ and
OH-. Thus, here's the only way I solve this and not violate conservation of
mass and charge, unless this is a quantum physics question:
+/-nH+ = H+
+/-ne- = OH-
+/-n = nothing
So, substituting, here's what we get:
M2Ox + H2O <--> M2Ox + OH¯ + H+
Well, this is hardly a mystery now, provided everything above was correct, and
it isn't particluarly informative. Does this demonstrate anything to me? No.
If you happen to know what this demonstrates, please let me know, otherwise
this just appears to be obfuscation and doesn't document the claim.
Mark claims that the anode is electrically neutral during the process. If it
is neutral, I can't imagine how it can generate a charge to create H+ ions,
and in fact this would appear to contradict conservation of charge laws. In
other technologies, usually the anode carries an electrical charge, but
granted, we don't know what is supposed to happen here.
The statement "What this reaction shows is that as the potential of the
system is changed the character of the anode switches back and forth among
the various oxides, hydrides, and hydroxides which the coating can form." is
rather difficult to evaluate. It seems to say that as the voltage across the
anode changes, the metal atoms aquire more charge and bond with additional
oxygen and hydroxide ions. This would seem to be the crux of the technology,
in that this modification of the composition of the electrode surfaces is
what makes nitrate reduction more likely than more predictable and likely
reactions generating oxygen and chlorine gas.
Right now, I am unable to say whether this molecular reorganization is
possible, and I am unable to say whether these changes may have any effect at
all on what molecules will be oxidized or reduced. Mark seems to believe
that the surface materials of the electrode act as a catalyst for
oxidation/reduction reactions, and I am unable to say right now whether this
phenomenon is possible. Any input any of you can provide regarding this
would be invaluable. If we cannot evaluate these claims, though, it does not
make it impossible to make some sort of judgement, though.
There are numerous processes that must precisely occur in order to make this
overall process work. If any one of these processes cannot happen, then the
entire process cannot happen. In order for upscale technologies to prove that
their system works, the burden is on them to substantiate all of these
individual processes, and for us to prove it cannot work we simply have to
refute one.
Greg
http://www.geocities.com/ResearchTriangle/.../2024/fish.html
To date, there has been no response from Upscale Technologies, either to my request for information to Ellen Lubin, or to my refutation of Mr. Lubin's assertions posted in rec.aquaria.tech. The silence from Upscale Technologies can be interpreted in many ways, but does little to counter the idea that this "N-Forcer technology" is infeasable and most likely impossible.
The N-Forcer on E-Bay
But, after a search on it, I came across the following site that shows the individuals from the company who make the N-Forcer responding back and forth with another individual who has "questions" regarding the capability of the N-Forcer.
Just thought I'd share. Any comments?
On March 22nd, 1999, I got the following unsolicited email regarding my technology review of the N-Forcer:
Ellen Lubin wrote:
> Hello Greg,
>
> I take issue with the "snake oil" comment. I'm going to be at Virginia
> Poly Tech on March 28-31 talking at a conference on Fundamentals,
> Modeling, and Applications of Nitrification and Dentrification in
> Wastewater Treatment why don't you stop by and learn about our
> technology before bad mouthing it. Stop by our Industrial site
> www.upscalewater.com and take a look at the mechanism that drives our
> technology. Our technology is denitrifying drinking water in Montana,
> wastewater treatment in Miami and we are being named Best Available
> Technology for Nitrate Removal by the EPA. Eventually every drop of
> water you drink, flush down your toilet and every drop of water used in
> manufacturing will be denitrified by our N-Forcer technology. You show
> your ignorance by talking before you know what you're talking about.
>
> If after reading about our technology you have any further questions I
> would be glad to educate you on denitrification.
>
> HAVE AN INFORMATIVE DAY!
>
> Ellen Lubin, VP Sales/Mkt
This is the reply I sent in March 24th. I have yet to get a response to this.
Ms. Lubin,
Based on the information you provided, and what was available on your
website, I am again reviewing your N-Forcer technology. I have several
questions regarding the information you provided that I hope you can clear
up for me.
I have looked through the EPA website in order to find documentation
regarding an endorsement of the N-Forcer technology by the EPA and was
unable to find it. A test protocol, dated May 11th, 1998 has been adopted
entitled "Protocol for Equipment Verification Testing for Physical Removal
of Nitrate", which contained test plans for reverse osmosis, ion exchange
and biological process, but no mention was made of electrochemistry. To
date, no information appears to be published endorsing any available
nitrate removal technology as far as I was able to determine, although it
is quite possible this has in fact been done and the information has not
yet been published on the web. I would imagine that your company has
issued a press release that would give me the information I need to track
down the verification.
I would be interested in finding out what municipality in Montana is
currently using N-Forcer technology, so I could contact them and hear their
results. Although they would be operating under very different conditions
than fishkeepers, their results would probably be helpful. I'm still
tracking down what's going on with the Miami/Dade County and hope to get
some information from them soon.
I worked through the chemistry to identify the effects of N-Forcer
technology on the pH of the water column. Using the formula provided in
the electrochemistry section of your web page, it appears that in reducing
a 5 ppm concentration of nitrate, it would produce a molar OH-
concentration of .0004838, and this would shift the pH of the water from
7.0 to 10.68. I am in the process of getting verification for these
calculations, but if you have a resource there that can confirm or debunk
these calculations your input would be helpful.
I looked at the program for the conference at Virginia Tech, and didn't see
you on the speaker's list. What's your talk about?
Greg Letiecq
Sometimes, silence can speak volumes...
After posting in rec.aquaria.tech for assistance in confirming these calculations and getting input on the feasability of this process, Mark Lubin decided to weigh in with this post on March 29th:
To all N-FORCER owners, but especially to the overly critical and the
critically ignorant…I guess that means you Greg Letiecq -
There's been a lot of banter in this forum recently about the chemistry and
technology behind the product you all know as the N-FORCER. There have been
comments about the technology and a large dose of opinionating about the moral
turpitude of this company's marketing staff and its advertising efforts.
As has been pointed out, the net reaction for nitrate reduction at the cathode
is:
2NO3¯ + 6H2O + 10e¯ --> N2 + 12OH¯
The analysis offered then proceeded to determine that the effect of this
system could only be to raise the pH to 10.99. This would be true only if
the system were sealed, contained no air above or dissolved in the water, and
contained only deionized water.
Further, and more importantly, the reaction above upon which Mr. Letiecq
builds his case as to the N-FORCER's devastating effects refers only to the
nitrate reduction reaction at the cathode. Nowhere in our literature,
advertisements, or on our web pages do we claim this is the only reaction
taking place. It should be apparent to anyone with even a modest knowledge
of chemistry that this is preposterous and would lead to both mass and
electron imbalance almost instantly.
When I and my marketing staff decided what was to go out, we saw no reason to
include a complete tutorial on all aspects of aquatic chemistry or
electrochemistry. Therefore, I will comment at this time on some other
aspects of the system's operation and address why the increase in pH
described simply does not occur.
* As I noted, the 10.99 pH value is only valid in a sealed, degassed, RO or DI
water system.
* The carbonate - carbon dioxide equilibrium system is one of the main
controllers of pH according to the following reaction, found in any beginning
aquatic chemistry book:
H2O + CO2 <--> H2CO3 <--> H+ + HCO3¯ pH varies from 6.0 to 8.4
* Production of ammonia by aerobic bacteria is an acidifying oxidation. The
hydrogen ions produced are on a 1:1 basis mole for mole with nitrite as
follows:
2NH3 + 3O2 --> 2NO2¯ + 2H2O + 2H+
* The ammonia consumes oxygen as above and the nitrite ion (NO2¯ ) so
produced is oxidized to nitrate ion (NO3¯ ) also by basically using up oxygen
as follows:
2NO2¯ + O2 --> 2NO3¯
* The oxygen used in both of these reactions is oxygen dissolved in the
water, not in the gaseous form. Aside from equilibrium with atmosphere,
there are two possible anodic reactions which occur in an N-FORCER at the
anode electrode (that's the one not taken into account during the so called
scientific analysis of our system):
2H2O --> O2 + 4H+ + 4e¯
4OH¯ --> 2H2O + O2 + 4e¯
* The proprietary mixed metal oxide coating on the anode electrode
participates in maintaining electrical neutrality and also generates some H+
ions to offset the OH¯ production as follows:
M2Ox + H2O <--> M2Ox +/- n +/-ne¯ +/-nH+
What this reaction shows is that as the potential of the system is changed the
character of the anode switches back and forth among the various oxides,
hydrides, and hydroxides which the coating can form.
* Since none of the conversions described above occur all at once the possible
effects on pH are avoided because the system has more than adequate time to
equilibrate by the various buffering mechanisms.
It appears to me that Mr. Letiecq has been trying to build himself a
reputation as an "expert" in the electronic media at UpSCALE's expense by
virtue of this type of analysis and product review, yet he admittedly does
not and has not owned one of our products at any time. I resent being called
a "snake oil merchant" by someone who tries to cover his rather thin
knowledge of chemistry by making a lot of ill-informed noise and who
proclaims as "impossible" what he doesn't have the capacity to understand.
In today's edition of Mr. Letiecq's newsletter he has, to his credit, finally
picked up a chemistry book. However, he is still missing the point…not all
moles of these substances are created, used, or need to be buffered at one
time.
Perhaps THE major fault in his reasoning and arguments is that simply because
he cannot find literature references to our process it must not exist. The
processes he says he did find occur in acidic water and I'm willing to bet
what he found were entries in the table of "electrochemical half-cell
potentials" from the Handbook of Chemistry & Physics or some other
compendium. The UPSCALE process is not in the literature because WE invented
it WE have not published it, so its not generally available for other people
to employ.
Mr. Letiecq's expert friends may be very knowledgeable in their respective
fields, but they are not the inventors of this technology and are not
equipped to comment on whether or not it is possible to consummate these
reactions. They are however, far more qualified than Mr. Letiecq will ever
be.
The famous British scientist, Lord Kelvin, once said:
"Condemnation without investigation is the height of ignorance"
Since Mr. Letiecq has based his "scientific" analysis on drawing conclusions
from advertising rather than science, I submit he should pay close attention
to this quote. He seems to be suffering from a large dose of the "N.I.H"
syndrome…"Not Invented Here".
Mark Lubin, President/CEO
Of course, this post warranted a response, which I posted on March 30th:
upscale@my-dejanews.com wrote:
> To all N-FORCER owners, but especially to the overly critical and the
> critically ignorant…I guess that means you Greg Letiecq -
Overly critical and critically ignorant. Well, I'll accept that. In my
experience, being critical of marketing claims until the technology is proven
is a wise course of action. As far as my ignorance, I am doing my best at
resolving that with the help of the members of this group, the library, and
friends of mine that have a far more thorough technical background. I
repeatedly ask for help in understanding this process, but unfortunately your
VP of marketing has failed to respond to my requests. My ignorance is as much
a product of the nonresponsiveless of your company as anything else.
At least now, however, we have an open discussion on the topic where we would
hope the truth can be found. I can hope for no better outcome, and if the
technology is sound and proven, I would darn well like to know it as we all
have nitrate management issues and are always looking for solutions. I honor
the truth.
We do apparently agree that the N-Forcer process does create a number of OH-
ions that would shift the pH of pure water. Whether the carbonate buffering
system present in most freshwater compensates for this shift is somewhat
irrelevant in that this only delays the shift in pH as the process continues.
At some point, the carbonate concentration will reach a point where the pH
will shift significantly upwards. With the great deal of OH- produced, this
point can be reached rather rapidly, depending on the buffering capacity that
exists. For someone like myself, who has relatively soft water in my
aquarium, I would fear this to happen sooner rather than later.
Likewise of limited relevance is the question of how we got the initial
concentration of nitrate, and what effect that process had. The nitrate
concentrations that I experience can in no way compansate for the shift the
N-Forcer process apparently performs, as the dissociation constant of a
nitrates is extrememely low compared to the near unity dissociation constant
of hydroxide, and for every mole of nitrate six moles of hydroxide is
apparently produced. So not only is nitrate a much weaker acid than
hydroxide is a base, but there is far more hydroxide produced than nitrate
removed.
I can't see any reason to believe that the introduction of 6 moles of OH- for
every mole of nitrate removed can NOT have an effect on water chemistry. I
have modeled the effect on a admittedly simplified system, but if it will
assuage the feelings of upscale technologies I can model a more complex system
to demonstrate essentially the same thing.
I do appreciate the information on the reactions at the anode, and will take a
look at them shortly to see what effect they have. When I have some
information on that, I will do my best to describe any mitigating effects.
Admittedly, we do not have access to anything describing the process that
actually occurs. It is not described in patent application #5614078. It is
not described in any available textbook, and I cannot find a single
scientific paper that describes it. It is science, that for the scientific
community does not exist as it has not been published, reviewed by peers, or
vetted in any way. With the protection available through patent law, it
would seem to be no threat to make known exactly how this miracle of
electrochemistry is supposed to occur, yet for some reason it remains a dark
mystery.
So I have to figure out what's going on based on what Upscale Technology
chooses to provide. I've done that. Now I am apparently ignorant for not
understanding something that is considered by Upscale Technology to be a
secret. Well, educate me, correct my calculations, give me the proper
formulas.
I suppose that in the end it is more a question of whether it works rather
than how it works, but to spend $300-$450 to purchase it in order to test it
is pretty much out of the question. Since there is nothing in the way of
test data available, the only option I have is to try to understand the
process that supposedly takes place and calculate the results as best I can.
Sure I'll make mistakes, and I welcome corrections.
Greg
http://www.geocities.com/ResearchTriangle/.../2024/fish.html
And after researching the assertions of Mr. Lubin, my conclusions were posted on March 31st:
As time permits, I'm trying to make some sense out of Mark Lubin's description
of the effects that occur at the anode of the N-Forcer unit, and about what's
going on with the metal-oxide surfaces of the anode and cathode. Again, I'm
looking for some help around this.
It would seem to make sense that impacts at the anode can and would offset
the effects we've identified at the cathode. If we add OH- ions at one, and
remove them at the other, it's possible that we end up with a neutral or at
least less drastic effect. At least it would appear that the determination
of the cathode effects is essentially accurate, as Mark seems to be in
agreement with those calculations.
At the anode, Mark points out two "possible" reactions. The first appears to
be simply water electrolysis, 2H20 -> O2 + 4H+ + 4 e-. There are several
issues that are problematic here.
The first problem is that this reaction is entirely contradictory to the
process described in the patent application for the technology (PN
5,614,078). In that document, Mark describes the negative impacts of other
implementations of electrolytic processes, at one point saying "since most
noble metals are excellent catalysts for the hydrogen ion reduction reaction,
the hydrogen evolution reaction will proceed at a reaction rate many times
larger than the nitrate reduction rate, causing the pH of the sea water to
increase beyond acceptable limits for marine life survival." Essentially,
that unless the process is modified in some way, large amounts of water will
be electrolized, causing a massive pH shift. Later on in the document, when
describing the process, Mark says "In addition, carbon fibers demonstrate
poor electro-catalytic behavior for hydrogen, oxygen and chlorine reactions.
The low potential required for nitrate reduction with carbon fibers also
helps to prevent any hydrogen, oxygen, and chlorine reactions."
So in the patent application, it would seem that Mark denies any appreciable
activity on electolyzing water, but in his statements to us here, he
would appear to claim it is an important balancing process to the demonstrated
reactions occuring at the cathode. Unless I have misunderstood, this is a
complete contradiction.
The other process he claims is "possible" 4OH- -> 2H2O + O2 + 4e-. While
this correctly balances for mass and charge, it seems somewhat unusual to me
that hydroxide ions would act this way. With all of the other substances in
the water available for reaction, that hydroxide ions would "implode" like
this to generate free electrons would appear to violate the laws of
thermodynamics for conservation of energy. I have not calculated it yet, but
the Gibbs free energy of the left hand side is probably far lower than the
Gibbs free energy on the right hand side since there are free electrons
there. Since reactions tend to move from higher to lower energies, this
seems backwards, and there is no indication that the anode can provide that
energy. The patent documents talk about low current densities as an
important feature of the process, so that would seem to make this abundance
of energy unavailable. I need additional input on this part especially, and
would welcome any help any of you out there can provide.
It would have been better if Mark had told us what actually is happening,
instead of what is possibly happening. It's takes a lot of effort to vet
these different possibilities, and even if one reaction is demonstrated to be
impossible, it's an easy thing to dismiss the results as we haven't actually
determined anything about what the system in actuality does.
The last piece of technical information was this:
"The proprietary mixed metal oxide coating on the anode electrode
participates in maintaining electrical neutrality and also generates some H+
ions to offset the OH¯ production as follows:
M2Ox + H2O <--> M2Ox +/- n +/-ne¯ +/-nH+
What this reaction shows is that as the potential of the system is changed the
character of the anode switches back and forth among the various oxides,
hydrides, and hydroxides which the coating can form."
I would assume that in this equation, "M" represents the proprietary metal
used in the metal oxide. What the "n" represents is a mystery, but hopefully
it's not too difficult to solve. Since we're talking about a generic
equation here, in english it would seem to read as 'Metal oxide and water
yield metal oxide and some stuff, some stuff with electrons, and some stuff
with protons' (H+ is a fancy way of saying proton).
In any reaction, there has to be conservation of mass and charge, so we can
subtract parts out and still have a valid equality, although that no longer
represents the process. If we subtract M2Ox from both sides, we get the
following equality:
H2O = +/- n +/-ne¯ +/-nH+
The "stuff" in water is pretty well documented. H2O can dissociate into H+ and
OH-. Thus, here's the only way I solve this and not violate conservation of
mass and charge, unless this is a quantum physics question:
+/-nH+ = H+
+/-ne- = OH-
+/-n = nothing
So, substituting, here's what we get:
M2Ox + H2O <--> M2Ox + OH¯ + H+
Well, this is hardly a mystery now, provided everything above was correct, and
it isn't particluarly informative. Does this demonstrate anything to me? No.
If you happen to know what this demonstrates, please let me know, otherwise
this just appears to be obfuscation and doesn't document the claim.
Mark claims that the anode is electrically neutral during the process. If it
is neutral, I can't imagine how it can generate a charge to create H+ ions,
and in fact this would appear to contradict conservation of charge laws. In
other technologies, usually the anode carries an electrical charge, but
granted, we don't know what is supposed to happen here.
The statement "What this reaction shows is that as the potential of the
system is changed the character of the anode switches back and forth among
the various oxides, hydrides, and hydroxides which the coating can form." is
rather difficult to evaluate. It seems to say that as the voltage across the
anode changes, the metal atoms aquire more charge and bond with additional
oxygen and hydroxide ions. This would seem to be the crux of the technology,
in that this modification of the composition of the electrode surfaces is
what makes nitrate reduction more likely than more predictable and likely
reactions generating oxygen and chlorine gas.
Right now, I am unable to say whether this molecular reorganization is
possible, and I am unable to say whether these changes may have any effect at
all on what molecules will be oxidized or reduced. Mark seems to believe
that the surface materials of the electrode act as a catalyst for
oxidation/reduction reactions, and I am unable to say right now whether this
phenomenon is possible. Any input any of you can provide regarding this
would be invaluable. If we cannot evaluate these claims, though, it does not
make it impossible to make some sort of judgement, though.
There are numerous processes that must precisely occur in order to make this
overall process work. If any one of these processes cannot happen, then the
entire process cannot happen. In order for upscale technologies to prove that
their system works, the burden is on them to substantiate all of these
individual processes, and for us to prove it cannot work we simply have to
refute one.
Greg
http://www.geocities.com/ResearchTriangle/.../2024/fish.html
To date, there has been no response from Upscale Technologies, either to my request for information to Ellen Lubin, or to my refutation of Mr. Lubin's assertions posted in rec.aquaria.tech. The silence from Upscale Technologies can be interpreted in many ways, but does little to counter the idea that this "N-Forcer technology" is infeasable and most likely impossible.
